Cosmetic composition for nails, free of phthalates, camphor and aromatic solvent

ABSTRACT

The cosmetic composition for nails without phtalate, without camphor or aromatic solvent comprises:  
     a principal cellulosic filmogenic polymer, preferably nitrocellulose,  
     a diester of benzoic acid with a diol, as a plasticizer,  
     and at least one additive resin.  
     This composition can be used as a colored nail polish or for providing an adherent layer or a clear finish layer.

[0001] The present invention relates to a cosmetic composition for the nails, without phtalates, without camphor and without aromatic solvents and its use as a colored polish or for processing with an adherent layer or with a clear finishing layer.

[0002] Typically, a formulation of nail polish comprises a basic filmogenic polymer, secondary polymers, one or more plastifiers and one or more solvents. The mixture can also contain pigments, suspension agents and additives such as anti-UV agents, wetting agents, hydrating agents and perfumes.

[0003] All these formulations seek to optimize characteristic such as: a well-rounded application, a short drying time and a very brilliant finish. The formulator thus tries to keep this appearance by giving the formulation also high resistance to radiation, to wear, to chipping, to detergents and to greases. This must result in good adherence and a good compromise between hardness and flexibleness of said polish.

[0004] Numerous solutions have been proposed to meet these various requirements. The principal problem to be solved is the plastification of the nitrocellulose which remains the principal resin used in nail polishes. These phtalates and camphor are good plasticizers, but must be replaced because of their toxicity. For identical reasons, the use of aromatic solvents must also be avoided.

[0005] The constraints on producing nail polishes without phtalates, without camphor, and without aromatic solvents, have as a result changed the balance and the compromise of these formulations. New plasticizers have been envisaged.

[0006] In patent applications EP-A-0 495 373, EP-A-0 613 676 and EP-A-0 613 677, the REVLON company discloses various di- and trimesters. In the application WO-A-9 820 843, the KIRKER company uses a specific plasticizer TXIB (2,2,4-trimethyl 1,3-pentanediol diisobutyrate). L'OREAL plasticizes nitrocellulose with cross-linked polyesters (EP-A-0 740 930) or uses a fluorinated citrate (FR-A-2 785 531).

[0007] Mixtures of plasticizers have also been proposed, for example a mixture of citrate and toluene sulfonamide (EP-A-0 894 490) , a mixture of sucrose benzoate and sulfonamide (U.S. Pat. No. 4,820,509), or else a mixture of sucrose acetate isobutyrate, butyl benzylbenzoate and glyceryl tribenzoate (U.S. Pat. No. 5,662,891).

[0008] In his tests, to obtain the best compromise between hardness, flexibility, drying, adherence and durability, the applicant has discovered that benzoic diesters of diols can preferably replace the phtalates.

[0009] These plasticizers permit particularly having, with cellulosic derivatives, properties of brilliance, flexibility, hardness and adherence that are very interesting for nails.

[0010] To this end, the cosmetic composition for the nails according to the invention, without phtalates, without camphor nor aromatic solvents, comprises:

[0011] a) a principal cellulosic filmogenic polymer (A),

[0012] b) a diester,(B) of benzoic acid with a diol,

[0013] (i) the benzoic acid being either unsubstituted benzoic acid, or benzoic acid substituted by one, two or three groups selected from: —CN, —SCN, —NO₂, —CI, —Br, —F, —OCH₃, —OC₂H₅, —OC₆H₅, —CH=CH₂, a C₁₋₆ alkyle branched or not, —CH₂CH=CH₂, —NO₂, —NH₂, —OH, —SH and —SO₂NH₂

[0014] (ii) the diol being selected from:

[0015] linear diols of the formula HO—(CH₂)_(n)—OH (1) in which n is a whole number between 4 and 20

[0016] diols of the formula HO—(CH₂)_(x)—A—(CH₂)_(y)—OH (II)

[0017] x and y being whole numbers from 0 to 4

[0018] A being an aromatic cyclic or a cycloaliphatic, if desired substituted with a linear or branched C₁₋₃₀ alkyl, or a

[0019] group

[0020] R₅ being a linear or branched alkyl radical of C₁ to C₄.

[0021] diols of the formula

[0022] R₁ being hydrogen, or a linear or branched C₁-C₄ alkyl radical

[0023] R₂ being hydrogen, or a linear or branched C₁-C₄ alkyl

[0024] R₃ being a linear or branched C₁-C₄ alkyl radical diols of the formula

[0025] BZ being a benzenic radical

[0026] c) at least one additive resin (C).

[0027] Preferably, the principal filmogenic polymer A is selected from nitrocelluloses, cellulose acetobutyrates, cellulose acetopropionates, cellulose ethers and mixtures of these. The preferred filmogenic polymer is nitrocellulose, in particular nitrocellulose of about 12%, soluble in esters and insoluble in alcohols. The preferred grades of nitrocellulose comprise from 120 to 130 cellobiose units.

[0028] The cellulose acetobutyrates or acetopropionates are often used in clear nail polish as a finish or when a crystalline appearance is sought. Cellulose ethers, in particular ethyl cellulose, can complement the polymers A above, to increase the plasticity of the composition.

[0029] The new plasticizer B, a diester synthesized from a diol and a benzoic acid, has properties equivalent or superior to those of phtalates, particularly as to the high power of dissolving the cellulosic polymers, in particular nitrocellulose. The preferred diesters are hexane diol dibenzoates (in- particular 1,6-hexandediol), trimethyl pentane diol (in particular 2,2,-4-trimethyl 1,3-pentanediol) and methyl propane diol (in particular di tert-butyl benzoate of 2-methyl 1,3-propanediol).

[0030] Preferably, resin C is selected from thermoplastic (meth)acrylic resins, polyester resins with or without fatty acids but without phthalic acid, condensates of toluene sulfonamide, vinyl resins, polyurethane resins and mixtures of these latter.

[0031] The resins, obtained by condensation of ethyl toluene sulfonamide with formaldehyde or with an epoxy compound, are the preferred resins to improve adherence, by increasing the polarity of the film. These resins, rich in solids, increase the dry extract of the polish and give it a better covering power and a better shape.

[0032] Other resins could be used for the same purpose: acrylic resins and polyesters. In the category of acrylics, there are acrylics, methacrylics and styrene/(meth)acrylics. The less soluble resins are preferred (methyl and ethyl) of low molecular weight. Certain acrylic resins modified with siloxane or fluoride groups can be added for their surface tension and radiation resistance.

[0033] The polyester resins are condensations of polyacids with polyols or polyethylene/polypropylene glycols. These resins can be modified with synthetic fatty acids or monoglycerides of vegetable oils. Phtalic anhydride, isophtalic acid and terephtalic acid as the di-acid are of course unavailable for cosmetic compositions without phtalates.

[0034] There are used short chain resins in oils (about 30%) with castor oil or a synthetic fatty acid of the type Cardura E of Shell. The polyesters cited in the CTFA as copolymers of adipic acid/neopentylglycol/ trimetallic anhydride or adipic acid/chdm/ma/neopentylglycol/trimetallic acid, are often used for nail polish compositions.

[0035] The preferred vinyl resins are high molecular weight copolymers of vinyl acetate/vinyl chloride partially hydrolyzed or vinyl terpolymer chloride/vinyl acetate/hydroxylethylacrylate. Polyvinyl butyrate can also be used.

[0036] Certain polyurethane resins, such as those described in the CTFA, give to nail polishes interesting properties, particularly as to the balance of hardness/flexibility.

[0037] Another plastifier can be added to dibenzoate B to modify a desired mechanical property. To this end, the composition according to the invention can also comprise other plastifiers and/or plastifying resins D of a molecular weight lower than about 1500.

[0038] Certain resins of low molecular weight are considered as external plasticizers because they plasticize the systems without dissolving the cellulosic resins. There can be cited polyester adipates, polyester sebacates or butyl acrylate resins.

[0039] Preferably, the composition according to the invention can also include at least one constituent E selected from colorants, pigments, fillers, suspension agents, anti-UV agents, anti-oxidant agents, active agents such as vitamins, proteins, vegetable, mineral and/or animal extracts, and any other conventional ingredient used in nail polish.

[0040] The pigments, fillers, artificial nacres, flakes and hard waxes such as modified or unmodified polypropylene waxes, are used to give color and decorative effects to the nail polishes.

[0041] Clays, hectorites or modified montmoriilonites, colloidal silicas, modified waxes, modified urea resins, serve in nail polishes as in paints, to modify the rheology of the systems so as to combine ease of application and holding of the particles in suspension.

[0042] Other additives such as silicone or fluorine compounds for surface tension and sliding properties, hard waxes of fine granulometry for anti-radiation characteristics, anti-UV compounds, wetting agents for the stability of the pigments, are added to modify certain quite specific properties.

[0043] Products with a therapeutic effect such as vitamins, anti-oxidants, oligo-elements, proteins, oils, can be introduced into certain nail polishes.

[0044] It has been discovered that the compositions whose sum of the components B+D (plastifiers) represents at least 2% by weight of the total composition, preferably about 6 to 12%, give the best results.

[0045] Similarly, the ratio between the filmogenic polymer A and the sum of the plasticizers B+D, A/(B+D) is preferably comprised between 0.2 and 5, preferably between 0.6 and 2.

[0046] Preferably, the composition according to the invention contains no formaldehyde. The resins are solubilized in non-irritating solvents, the composition comprising at least one solvent selected from ethyl acetate, butyl acetate, propyl acetate, di-isobutyl acetate, ethanol, isopropanol and mixtures of these. Other solvents such as diacetonealcohol, methoxypropanol and certain ketones can be added to adjust the speed of evaporation and drying.

[0047] Rheological agents that can be added to the composition according to the invention are preferably selected from modified clays of the montmorillonite or hectorite type, hydrophilic or hydrophobic pyrogenated silicas, modified waxes, modified urea resins and mixtures of these.

[0048] The production of these nail polishes is carried out in a conventional manner, according to the conventional operative mode comprising the following consecutive steps:

[0049] dissolution of the resins, plasticizers and various additives in solvents,

[0050] dispersion of possible Theological agents in these solutions,

[0051] dispersion of the pigments and coloring materials in these solutions,

[0052] preparation of a base by mixing the solutions and possible complementary rheologic agents,

[0053] preparation of colors by adding to this base pigment dispersions, nacres and flakes according to the colorometric standard,

[0054] inspection of these products before packaging.

EXAMPLES

[0055] The present invention is illustrated by the examples of the following formulations (all the percentages are expressed by weight of the dry composition):

Example 1 (comparative)

[0056] Formula according to the prior art with phtalate and camphor, without formaldehyde and without aromatic solvents Nitrocellulose (12.1%) 10.6 Polyester resin 4.6 Dibutyl phtalate 4.8 Camphor 1.4 Solvents 75.2 Stearalkonium hectorite 0.9 Pigments 2.5

Example 2 (comparative)

[0057] Formula according to the prior art with phtalate, camphor and formaldehyde, without aromatic solvents Nitrocellulose 10.6 Tosylamide/formaldehyde 4.6 Dibutyl phtalate 4.8 Camphor 1.4 Solvents 75.2 Stearalkonium hectorite 0.9 Pigments 2.5

Example 3

[0058] Formula without phtalates or camphor, without formaldehyde and without aromatic solvents Nitrocellulose 10.5 Hexanediol dibenzoate 8.1 Acrylics 1.5 Polyester 4.2 Tosylamide epoxy 3.0 Solvents 68.3 Stearalkonium hectorite 1.0 Pigments 3.4

Example 4

[0059] Formula without phtalates or camphor, without aromatic solvents and with formaldehyde Nitrocellulose 10.0 Hexanediol dibenzoate 7.2 Acrylics 1.5 Tosylamide/formaldehyde 5.2 Polyester 3.0 Solvents 63.7 Stearalkonium hectorite 1.0 Pigments 3.4

Example 5

[0060] Formula without phtalates or camphor, without formaldehyde and without aromatic solvents Nitrocellulose 14.5 Trimethyl pentanediol dibenzoate 13.1 Solvents 68.0 Stearalkonium hectorite 1.0 Pigments 3.4

[0061] The various nail polishes, having the above compositions, are prepared according to the conventional operative mode described in the introduction.

[0062] The characteristics of a nail polish being difficult to measure directly on the nails, tests are carried out by comparison on other surfaces such as glass or aluminum (qualicoat quality 5004 H 24).

[0063] The films are applied with the help of a Conway applicator to a wet thickness of 100 micrometers.

[0064] Drying is measured on a plate at 35° C. with a trace which leaves a rotating sphere on the nail polish applied wet at 100 micrometers on a Leneta type cardboard.

[0065] The physical tests are carried out after drying overnight at 20° C. or. for 2 hours at 50° C.

[0066] The thicknesses are measured on aluminum according to the ISO 2360 standard.

[0067] The brilliance is measured with a brilliantometer at an angle of 60° according to the ISO 2813 standard.

[0068] The hardnesses are measured on glass with a persoz pendulum according to the ISO 1522 standard.

[0069] The flexibility of the film is tested on aluminum with a cylindrical 3 mm mandrel according to the ISO 1519 standard.

[0070] Tests of radiation, wear as well as strength under wet abrasion, can be carried out with an apparatus for the washability of paints as descried in the AFNOR T 30 082 standard.

[0071] Adherence is compared on glass with the quadrillage method, on a cutout film with a comb having teeth spaced 1 mm apart, according to tearing off of an adhesive strip (cf. ISO 2409 standard).

[0072] A final test of durability on the nails is arranged for a group of women to evaluate the brilliance, wear and chipping.

[0073] For formulations 1 to 5, the principal results are the following: No. 1 No. 2 No. 3 No. 4 No. 5 Drying 4.25 min 3.5 min 2.5 min 3.0 min 3.5 min Hardness 260 sec 230 sec 200 sec 195 sec 210 sec Adherence 0/1 0 0/1 0 0/1 (0 to 5) Flexibility Passing Passing Passing Passing Passing (3 mm Cyl.) Time on the 2.9 days 3.4 days 3.1 days 3.6 days 3.5 days nails

[0074] It has bee discovered that compositions 3, 5 and 4, respectively without formaldehyde and with formaldehyde, give results superior to the corresponding compositions 1 and 2, particularly as to the duration on the nails (at least +0.2 day, even +0.6 day for composition No. 5) with a shortened drying time.

[0075] Moreover, the compositions according to the invention including hexanediol dibenzoate or trimethyl pentane diol dibenzoate give more brilliant nail polishes. 

1. Cosmetic composition for fingernails, without phtalate, without camphor or aromatic solvent, comprising: a principal cellulosic filmogenic polymer (A), a benzoic acid diester (B) with a diol, (i) the benzoic acid being either unsubstituted benzoic acid, or benzoic acid substituted with one, two or three groups selected from: —CN, —SCN, —NO₂, —CI, —Br, —F, —OCH₃, —OC₂H₅, —OC₆H₅, —CH=CH₂, a C₁₋₆ alkyle branched or not, —CH₂CH=CH₂, —NO₂, —NH₂, —OH, —SH and —SO₂NH₂ (ii) the diol being selected from: linear diols of the formula HO—(CH₂)_(n)—OH (1) in which n is a whole number between 4 and 20 diols of the formula HO—(CH₂)_(x)—A—(CH₂)—OH (II) x and y being whole numbers from 0 to 4 A being an aromatic cyclic compound or a cycloaliphatic compound, if desired substituted with a: linear or branched C₁₋₃₀ alkyl, or a

group R₅ being a linear or branched C₁ to C₄ alkyl radical diols of the formula

R₁ being hydrogen or a linear or branched C₁-C₄ alkyl radical R₂ being hydrogen or a linear or branched C₁-C₄ alkyl radical R₃ being a linear or branched C₁-C₄ alkyl radical diols of the formula

BZ being a benzenic radical at least one additive resin (C).
 2. Composition according to claim 1, characterized in that the polymer A is selected from nitrocellulose, cellulose acetobutyrate, cellulose acetopropionate, cellulose ethers and mixtures of these.
 3. Composition according to any one of claims 1 or 2, characterized in that the resin C is selected from thermoplastic (meth)acrylic resins, polyester resins with or without fatty acids, toluene sulfonamide condensates, vinyl resins, polyurethane resins and mixtures of these.
 4. Composition according to one of claims 1 to 3, characterized in that it comprises other plasticizers and/or plasticizing resins D of a molecular weight lower than about
 1500. 5. Composition according to one of claims 1 to 4, characterized in that it includes at least one constituent E selected from colorants, pigments, fillers, suspension agents, anti-UV agent, anti-oxidant agents, active ingredients such as vitamins, proteins, vegetable, mineral and/or animal extracts.
 6. Composition according to one of claims 4 and 5, characterized in that the sum of constituents B+D represents at least 2% by weight of the total composition, preferably about 6 to 12%.
 7. Composition according to one of claims 1 to 6, characterized in that the principal filmogenic polymer A is nitrocellulose.
 8. Composition according to one of claims 4 to 7, in which the ratio between the filmogenic polymer A and the sum, of the plasticizers B+D, A/(B+D) is comprised between 0.2 and 5, preferably between 0.6 and
 2. 9. Composition according to one of claims 1 to 8, characterized in that it contains no formaldehyde.
 10. Composition according to one of claims 1 to 9, characterized in that the component B is dibenzoate of 2,2,4-trimethyl 1,3-pentane diol.
 11. Composition according to one of claims 1 to 9, characterized in that component B is a hexane diol dibenzoate.
 12. Composition according to one of claims 1 to 9, characterized in that the component B is 2-methyl 1,3-propanediol tert-butyl benzoate.
 13. Composition according to one of claims 1 to 12, characterized in that the resin C is a condensation resin between ethyl toluene sulfonamide and formaldehyde or a condensation resin between ethyl toluene sulfonamide and an epoxy compound.
 14. Composition according to one of claims 1 to 13, characterized in that the resin C is a polyester without phtalic acid.
 15. Composition according to one of claims 1 to 14, characterized in that it comprises at least one solvent selected from ethyl acetate, butyl acetate, propyl acetate, isobutyl acetate, ethanol, isopropanol and mixtures of these.
 16. Composition according to one of claims 1 to 15, characterized in that it comprises Theological agents selected from modified clays of the montmorillonite or hectorite type, hydrophilic or hydrophobic pyrogenated silicas, modified waxes, modified urea resins and mixtures of these.
 17. The use of the composition according to one of claims 1 to 16 as nail polish, applied alone, or in several layers.
 18. The use of the composition according to one of claims 1 to 17 for primary adherence to the nails.
 19. The use of the composition according to one of claims 1 to 18 as a finishing layer, or as an intermediate layer on the nails. 